Method of manufacturing a boot seal

ABSTRACT

The present invention resides in a boot seal for use in sealing a joint. The joint comprises first and second relatively movable parts. The boot seal is configured in the form of a sleeve to extend between and around the vehicle relatively movable parts. The sleeve has a laminate wall which comprises at least two layers of thermoplastic elastomeric material which are bonded together. At least one of the layers is a stretch-toughenable polyester thermoplastic elastomer which has been diametrically stretched in an amount effective to increase the toughness of said one layer. The laminate wall has a percent elongation to rupture of at least 100, and a flexural modulus which is less than 100,000 psi. The laminate wall preferably has a puncture resistance of at least 50 Newtons/mm wall thickness.

RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.09/564,654, filed May 3, 2000 now U.S. Pat. No. 6,386,551, which is acontinuation-in-part of U.S. patent application Ser. No. 08/811,672,filed Mar. 5, 1997 (now U.S. Pat. No. 6,234,488) and also corresponds toContinuation application Ser. No. 09/602,226, filed Jun. 23, 2000 (nowU.S. Pat. No. 6,322,085), and assigned to the assignee of the presentapplication.

FIELD OF THE INVENTION

The present invention relates to a vehicle steering or suspensionsystem, and particularly relates to a boot seal for sealing a movablejoint in a vehicle steering or suspension system.

BACKGROUND OF THE INVENTION

Boot seals are used to protect the bearings in joints between relativelymovable parts of vehicle steering and suspension systems. The boot sealsare typically formed of a thermoplastic or thermosetting elastomer.Examples of prior art elastomers are neoprene rubber, a blend ofethylene-propylene rubber and polypropylene marketed by Monsanto Companyof St. Louis, Mo. under the trademark SANTOPRENE, and HYTREL polyestermarketed by E.I. DuPont de Nemours Co.

The boot seals are typically blow molded into the configuration in whichthey are to be installed, and are snapped into place in an interferencefit which is secured by metal clips.

Boot seal failure can be caused by fatigue, punctures, cuts or tears,and abrasive wear. Boot seal failures are a common cause of jointfailure. If a boot seal fails, water and dirt can get into the joint,and/or grease can leak out. It is desirable to increase the resistanceof boot seals to failure.

SUMMARY OF THE INVENTION

The present invention resides in a boot seal for use in sealing a joint.The joint comprises first and second relatively movable parts. The bootseal is in the form of a sleeve which extends between and around thevehicle relatively movable parts. The sleeve has a laminate wall whichcomprises at least two layers of thermoplastic elastomeric materialwhich are bonded together. At least one of the layers is astretch-toughenable polyester thermoplastic elastomer which has beendiametrically stretched in an amount effective to increase the toughnessof the one layer. The laminate wall has a percent elongation to ruptureof at least 100, and a flexural modulus which is less than 100,000.

Preferably, the laminate wall has a puncture resistance of at least 50Newtons/mm wall thickness.

Preferably, the stretch toughened one layer is a stretch-toughenablepolyester material which is resistant to dimensional change when exposedto heat.

Preferably, the boot seal is a laminate of a first outer layer which isformed of a stretch-toughened polyester material and a second innerlayer which is formed of a thermoplastic elastomer, wherein the outerlayer polyester material has a generally higher degree of toughness anda greater resistance to hydrocarbon chemicals than the inner layerthermoplastic elastomer, and wherein the inner layer thermoplasticelastomer has a higher degree of flexibility and softness than the outerlayer polyester thermoplastic material.

In an embodiment of the present invention, the inner layer thermoplasticelastomer is a polyolefin.

The present invention also resides in a process for making a boot seal.Two thermoplastic elastomeric raw materials are obtained and fedseparately into an extruder. The raw materials are separately extrudedfrom the extruder as coaxial tubular molten streams having an outsidediameter D₁ into a mold cavity comprising a corrugated inner wall havingan inside diameter D₂. The molten streams of thermoplastic elastomericmaterial are vacuum expanded against the mold cavity inner wall and thencooled to a semi-solid state while vacuum held against the mold cavityinner wall. The amount of expansion (D₂/D₁) preferably is in the rangeof about 200% to about 700%. One of the raw materials is a polyesterthermoplastic elastomer which is stretch toughenable by said vacuumexpansion and which when cooled has a percent elongation to rupture ofat least 100 and a flexural modules less than 100,000 psi.

The boot seal preferably has a puncture resistance of at least 50Newtons/mm thickness of the boot seal.

The thicknesses of the molten streams of thermoplastic elastomericmaterial are preferably controlled to achieve a boot seal wall thicknessin the range of about 0.6 to about 2 mm.

In a preferred embodiment of the present invention, the mold cavity isdefined by an endless series of movable molds, each mold having an openclamshell configuration prior to the point of extrusion, and a closedclamshell configuration after extrusion, the extrusion being continuous.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other features of the present invention will becomeapparent to one skilled in the art to which the present inventionrelates upon consideration of the following description of the inventionwith reference to the accompanying drawings, in which:

FIG. 1 is a sectional view of a boot seal in accordance with the presentinvention;

FIG. 2 is an enlarged sectional view of a portion of the boot seal ofFIG. 1;

FIG. 3 is a partial sectional broken view of a movable joint of avehicle steering system employing the boot seal of FIG. 1;

FIG. 4 is a schematic elevation view of a forming apparatus for makingthe boot seal of FIG. 1;

FIG. 5 is an enlarged detailed section view taken along line 5—5 of FIG.4;

FIG. 6 is an enlarged detailed section view taken along line 6—6 of FIG.4;

FIG. 7 is an enlarged detailed sectional view of an extruder die inaccordance with an embodiment of the present invention;

FIG. 7A is an enlarged detailed sectional view of the extruder head ofthe extruder die of FIG. 7;

FIG. 7B is an enlarged detailed sectional view of a variable nozzleextruder head in a forming apparatus;

FIG. 7C is an enlarged sectional view of a portion of FIG. 7B;

FIG. 7D is the enlarged sectional view of FIG. 7C following vacuumforming; and

FIG. 8 is a schematic illustration showing interaction of the extruderof FIG. 7 with a portion of the forming apparatus of FIG. 4.

DESCRIPTION OF ONE SPECIFIC PREFERRED EMBODIMENT OF THE INVENTION

Referring to FIG. 1, the boot seal 12 of the present invention is asleeve-like member formed of a flexible thermoplastic material. The bootseal 12 has a small diameter first end 14 and a larger diameter secondend 16. The boot seal 12 between ends 14 and 16 has an intermediateportion 18 which is corrugated. The diameters of the first and secondends and the distances between the peaks and valleys of the corrugationsare not critical, and are dictated by the particular dimensions of theapplication with which the boot seal is used.

FIG. 2 shows that the boot seal 12 has a laminate constructioncomprising a first ply 20, a second ply 22, and an adhesive bondinglayer 24 between the first and second plies 20 and 22. The adhesivebonding layer 24 is optional and dependent upon the compositions of theelastomeric materials used in the first and second plies 20 and 22.Certain plastics when in a molten state can bond together without theneed of an intermediate adhesive bonding layer. This laminateconstruction extends the full length of the boot seal 12.

The boot seal 12 of FIG. 1 is particularly useful with a ball and jointconstruction for a vehicle steering or suspension apparatus 30, asillustrated in FIG. 3. Referring to FIG. 3, the apparatus 30 comprises aball stud 32 and a housing 34. The stud 32 has a ball end 36 located ina socket 38 of the housing 34. The stud 32 further has a shank 40projecting longitudinally from the ball end 36. The shank 40 isconnectable with a movable part of a vehicle steering or suspensionapparatus in a known manner. The housing 34 has a shank 42 which isconnectable with another movable part of the steering or suspensionapparatus in a known manner. A bearing 44 is located in the socket 38,and supports the ball end 36 of the stud 32 for limited movementrelative to the housing 34.

The boot seal 12 in the form of a sleeve around the apparatus 30 shieldsthe bearing 44, the housing 34, and the ball end 36 of the stud 32 fromdirt and other foreign substances. A first clamp 50 holds the small end14 of the boot seal 12 firmly against the stud shank 40. A second clamp52 similarly holds the large end 16 of the boot seal 12 firmly against aseal ring 54 which is operatively associated with housing shank 42. Theflexible intermediate portion 18 of the boot seal 12 deflects betweenthe boot seal ends 14 and 16 upon movement of the ball stud 32 relativeto the housing 34. The relative movement is pivotable but can also belongitudinal to a limited extent depending upon the particular design ofthe steering or suspension apparatus. A lubricant (not shown) for thebearing 44, such as grease or the like, may be contained within thespace 56 enclosed by the intermediate portion 18 of the boot seal 12.

The corrugated boot seal 12 (FIGS. 1 and 2) is formed of a laminatedflexible thermoplastic elastomeric material. Preferably, the boot seallaminate structure, shown in FIG. 2, in one embodiment of the presentinvention, comprises an inner ply 20 which may be formed of a selectedthermoplastic for flexibility and softness. The outer ply 22 is formedof a polyester thermoplastic elastomer for toughness and resistance tohydrocarbon chemicals.

A preferred polyester thermoplastic elastomer for the outer ply 22 is acopolyester resin marketed by Eastman Chemical Products, Inc. under thetrademark ECDEL. ECDEL is believed to be a cycloaliphatic thermoplasticcopolyester (a copolyester-ether); more specifically, a condensationproduct of the trans isomer of 1,4-dimethyl-cyclohexanedicarboxylateunits, of cyclo-hexanedimethanol units and hydroxy terminatedpolytetramethylene ether glycol units. It is related to polyethyleneterephthalate (PET).

A preferred grade of ECDEL for the present invention is 9967. ECDEL 9967has a melt temperature of 205° C. to 230° C. (400° F. to 445° F.).

ECDEL 9967 is related to and has many of the same properties aspolyethylene terephthalate (PET). Polyethylene terephthalate (PET) isstretch-toughenable which makes it suitable for use in the manufactureof blow molded bottles. Primarily, ECDEL 9967 is alsostretch-toughenable. Stretching the plastic, for instance about 200% toabout 700%, allows the formation of thinner, more uniform side walls,but in addition causes a molecular orientation in the plastic whichdramatically increases the strength and barrier properties of ECDEL9967.

Unlike polyethylene terephthalate (PET), however, ECDEL was found tohave more flexibility. Stretched polyethylene terephthalate (PET) is avery rigid material, as it has to be for use in blow molded bottles. Itsflexural modulus (as determined by ASTM method D790) is about 450,000psi. ECDEL 9967 in contrast has a flexural modulus of about 21,750 psi.

ECDEL 9967, in addition, has other beneficial properties. It has apercent elongation to break of about 400. The percent elongation tobreak is determined using ASTM method D638. In this test, specimensabout 3 mm (⅛ in.) thick are tested using a crosshead speed of 508 mm(20 in.) per min. The percent elongation test is conducted at about 23°C. (73° F.) and 50% RH.

The flexibility and stretchability of ECDEL 9967 make this polyesterparticularly useful for the manufacture of boot seals.

ECDEL 9967 also has and a high degree of puncture resistance (PR)depending upon the amount stretched.

The resistance to puncture is measured on 50 mm×50 mm (2×2 inch)specimens of boot seal samples using a load cell and a steel rod probe.The probe has a working end which is finished to a radius of 3.28 mm(0.134 inch). The load cell is assembled with an Instron tensile testingmachine. A 760 gram ram is allowed to free fall 400 mm to force the testsamples to be punctured by the steel rod probe. The maximum tensileforce exerted by the probe free fall on the specimens is recorded inNewtons. This force is divided by the wall thickness (the minimum wallthickness if the specimen wall thickness varies), to obtain the punctureresistance.

Extrusion molded samples of ECDEL stretched about 320% were found tohave a puncture resistance of about 130 to about 150 Newtons per mm.Even moderate stretching of about 20% was found to provide beneficialstretch properties.

There are a number of thermoplastic polymers that arestretch-toughenable. For instance, polyethylene terephthalate (PET)mentioned above, and also polypropylene, styrene acrylonitrile andpolyvinyl chloride (PVC) are stretch-toughenable. However, polypropyleneand styrene acrylonitrile, as with polyethylene terephthalate (PET), arevery stiff following stretching and have flexural moduli of about245,000 and 490,000 psi, respectively. Polyvinyl chloride followingstretching retains some flexibility, but its percent elongationproperties prevent it from being used successfully in boot sealapplications.

Based on the above information and other data, it has been determinedthat the laminated boot seals of the present invention should be madeusing at least one ply of a stretch-toughenable polyester thermoplasticelastomer in which the boot seal is stretched an amount effective toachieve a puncture resistance of at least 50 Newtons/mm wall thickness,the elastomer at the same time having a flexural modulus which is lessthan 100,000 psi and a percent elongation to rupture of at least 100.

The inner ply 20 of the boot seal 12 preferably is a material which issofter than the outer ply 22. A softer inner ply 20 better accommodatessurface micro-roughness and imperfections of the linkage with which theboot seal 12 is used, thereby improving the sealability of the seals 12with the linkage. A preferred inner ply is a polyolefin. Polyolefinsalso have more flexibility than polyesters. This enhances theflexibility of the boot seal 12.

A preferred polyolefin for the inner ply is a polyether resin marketedby Eastman Chemical Products, Inc. under the trademark MXSTEN. Thispolyolefin is a polyethylene resin used primarily in the packagingfield. However, other polyolefins which are extrusion moldable, or anyflexible extrudable film forming material which is soft and bondablewith a polyester resin such as a polyurethane, can be used as the innerply 20.

An advantage in the use of MXSTEN is that it is stretch toughenablesimilar to ECDEL.

The inner ply 20 need not be a polyolefin or similar soft extrudablematerial, such as a polyurethane. For instance, boot seals in accordancewith the present invention can be made wherein both plies 20 and 22 areECDEL polyester. However, this may require linkage surfaces essentiallyfree of surface micro-roughness.

It is also possible to use an inner ply 20 of ECDEL wherein the ECDEL isblown or sponged. This is accomplished using conventional blowing agentsand procedures. By using blown ECDEL in the inner ply 20, the inner plyis made softer so that it has softness properties similar to those of apolyolefin. Thus, it is usable with surfaces having micro-roughness andimperfections. At the same time, the inner ply 20 has strengthproperties of stretch-toughened ECDEL.

Similarly, the outer ply 22 need not be 100% polyester thermoplasticelastomer. Boot seals in accordance with the present invention have beensuccessfully made wherein the outer ply 22 contains a substantial weightpercentage MXSTEN. The ECDEL present in the outer ply 22 even in smallamounts, when stretch-toughened, offers superior puncture resistance.

The advantage in incorporating an amount of MXSTEN in the outer ply 22as well as in the inner ply 20 is that it enhances the bonding strengthof the outer ply 22 to the inner ply 20.

When the outer ply 22 is substantially a polyester thermoplasticelastomer and the inner ply 20 is substantially a polyolefin, it may bedesirable to co-extrude with the plies 20 and 22 an intermediateadhesive bonding layer, designated layer 24 in FIG. 2. Suitableextrudable thermoplastic adhesives are well known. One is TIE BONDTL-905 marketed by Shell Chemical Company. Another is ADMER QB520Amarketed by Mitsui Chemical Company. When both plies 20 and 22 containcompatible plastics, for instance substantial amounts of MXSTEN in bothplies, or substantial amounts of ECDEL in both plies, then no adhesivemay be necessary. The plies may be self-bonding.

The corrugated boot seal 30 preferably is formed in a continuousextrusion/molding process as disclosed in FIG. 4. Both ECDEL and MXSTENare extrudable plastics. The process of FIG. 4 will be described for themanufacture of a laminate comprising an outer ply of ECDEL and an innerply of MXSTEN, bonded together by an adhesive bonding layer. Referringto FIG. 4, the ECDEL resin is fed into one hopper 110 for introductioninto the process, and MXSTEN resin is fed into a second hopper 112 forintroduction into the process. The resins flow to a heated extruder 114in separate chambers (not shown in FIG. 4), and then as separate flowsof molten plastic into an extruder die 116. The extruder die 116comprises concentric separate pathways, to be described, which introduceconcentric layers of molten plastic into a corrugator 118.

Simultaneous with the above steps, an adhesive is fed into a thirdhopper 120, and from there into the heated extruder 114 for flow throughthe extruder die 116 as a molten stream between the concentric layers ofECDEL and MXSTEN.

The corrugator 118 is a continuous vacuum corrugator manufactured byCullom Machine Tool & Die, Inc. of Cleveland, Tenn. The machine isdisclosed in U.S. Pat Nos. 4,439,130 and 5,257,924 incorporated byreference herein. Cullom Machine Tool & Die, Inc. is also the owner ofU.S. Pat Nos. 4,486,929; 4,718,844; 5,494,430; 5,645,871; 5,059,109;5,489,201; and 5,531,583; all disclosing subject matter relating to thatof the '130 and '924 patents, also incorporated by reference herein.Another patent containing relevant subject matter is U.S. Pat No.4,319,872 incorporated by reference herein.

The corrugator 118 comprises a continuous series of mold blocks 152which travel in a counterclockwise direction, in the view of FIG. 4, onan inner track 124. The track 124 has a forward run 122 which extendsfrom near the extruder 116 for essentially the full length of the lowerarea of the corrugator, and a return run 126 which extends foressentially the full length of the upper area of the corrugator. Thecorrugator 118 comprises transition areas 130 and 132 between theforward and return runs 122 and 124.

As shown in FIG. 4, molded plastic tubing 127 exits continuously fromthe forward run 122 and is passed to a cutter 134 which cuts the tubinginto boot seals 12 of desired lengths.

Further details of the corrugator 118 are shown in FIGS. 5, 6 and 7.

Referring to FIG. 5, which is an enlarged, detailed section view of thecorrugator 118 in the forward run 122 (FIG. 4), the track 124 ofcorrugator 118 (FIG. 5) comprises a pair of internal rails 142 and 144that extend continuously around the inside of the corrugator 118.Carriage rollers 146 and 148 are received into the rails 142 and 144.The carriage rollers 146 and 148 are mounted on the ends of a shaft 150which in turn supports mold block 152. Multiple mold blocks 152 areconnected together in a continuous series around the corrugator, asshown in FIG. 4. The mold blocks 152 are each comprised of clam-shapedmold halves 154 and 156. In FIG. 5, the mold halves 154, 156 are in aclosed position with the halves being brought together by the cammingaction of guide rollers 158 and 160 against cam surfaces 162 and 164.

Referring to FIG. 6, which is an enlarged, detailed section view of thecorrugator 118 in the return run 126 (FIG. 4), the clam-shaped moldhalves 154 and 156 are pivoted apart, on pivot center 158 (FIG. 6), sothat each mold block 152 is in an open position. In FIG. 6, the moldhalves 154 and 156 are pivoted into the open position by cam surfaces162 and 164 acting on guide rollers 158 and 160.

Referring back to FIG. 4, the mold halves 154 and 156 are in the closedposition of FIG. 5 for essentially the full extent of the forward run122, and in the open position of FIG. 6 for essentially the full extentof the return run 126. In the transition areas 130 and 132, the moldhalves pivot from the closed position of FIG. 5 to the open position ofFIG. 6, and vice versa, respectively.

Details of one embodiment of the extruder die 116 are shown in FIG. 7.The extruder die 116 in the embodiment of FIG. 7 is adapted for theco-extrusion of two layers, an inner ply 20 and an outer ply 22. Insteadof two layers, the extruder die 116 can be adapted readily for theextrusion of three layers which would include an intermediate adhesivebonding layer 24 between the inner and outer plies 20 and 22.

Referring to FIG. 7, the extruder die 116 comprises a die block 170. Thedie block has a first passageway 172 for the outer ply 22, and a secondpassageway 174 for the inner ply 20. Passageways 172 and 174 arecoaxial. Molten plastic introduced in ports 176 feeds the firstpassageway 172 and molten plastic introduced into port 178 feeds thesecond passageway 174.

Referring to FIG. 7A, it can be seen how coaxial molten plastic streamsexit from the first and second passageways 172 and 174 of the extruderdie 116.

FIG. 8 shows the interaction of the extruder die 116 with mold blocks152. Portions of three mold blocks 152 are shown in FIG. 8, from left toright, mold blocks 152 a, 152 b, and 152 c. In the closed position ofFIG. 5, the clam-shaped mold halves 154 and 156 are closed to define amold cavity 180. The leftmost mold block 152 a is cammed to an openposition so that the clam-shaped mold halves 154 and 156 (invisible inFIG. 8) embrace the extruder 116 which extends axially into thecorrugator forward run 122 (FIG. 4), on axis 122 a (FIG. 8) of theforward run. The mold block 152 b is cammed to a partially closedposition, and mold block 152 c to a fully closed position. Moltenplastic is introduced into the mold block cavity 180 when theclam-shaped mold halves 154 and 156 are nearly fully closed.

When the mold blocks 152 are fully closed, a vacuum is drawn in the moldblock inner wall 182 (FIGS. 5 and 8) to expand the extruded plasticdiametrically against the inner wall 182. The mold block halves 154 and156 have a plurality of slits 184 (FIG. 6) disposed in the grooves 186(FIG. 6) of the corrugated inner walls 182 thereof. Each of the slits184 communicates with one of a plurality of bores 188. The bores 188extend longitudinally through the mold halves 154 and 156 andcommunicate with a continuous circular vacuum header 190 (FIG. 6). Thevacuum header 190 is, in turn, in communication with a vacuum manifold192 (FIG. 5) which is maintained under vacuum. This communication ismaintained for the entire lower run of the corrugator along which themold blocks 152 are cammed to a closed position. The vacuum transmittedto the slits 184 of the mold halves 154 and 156 expands the extrudedtube of plastic outwardly against the mold block inner wall 182 into theconfiguration of a continuous corrugated tubular member, as shown inFIG. 1.

At the point of extrusion, the thermoplastic as received is at anelevated temperature, dependent upon the plastic used, in order to makethe thermoplastic pliable and susceptible to molding. It is desirable tocool the thermoplastic while it is in its expanded state. This isaccomplished by means of air plenums 194 (FIG. 5) which extend along thesides of the corrugator 118, for the full length of the forward run 122.The air plenums 194 communicate with a source of pressurized air (notshown). The plenums 194 lead to a pair of arcuate shields 196 whichembrace the mold blocks 152 moving in the forward run, in a spacedrelationship with the mold blocks 152, to define an annular air chamber198. Cooling air is introduced continuously into the annular air chamber198 to cool the mold blocks 152.

The ECDEL and MXSTEN resins are particularly advantageously used in thevacuum molding process of the apparatus of FIGS. 4-8, as they arecontinuously extrudable, are stretch-toughenable in the vacuum expansionprocess, and form a rigid enough ply, when cooled, to cut.

The following examples illustrate the present invention.

EXAMPLE 1

A boot seal 12 (FIG. 1) was manufactured using the apparatus of FIGS.4-8. The boot seal had a laminate construction comprising an outer plyof ECDEL, an inner ply of MXSTEN, and an intermediate adhesive plymarketed by Shell Chemical Company under the tradename TIE BOND TL-905.

In the manufacturing step, the pelletized materials were introducedseparately into the extruder 114 where they were reduced to a moltenstate. The molten materials were extruded as a 3-ply hollow laminate ata temperature slightly above 225° C. (437° F.). The melting point ofECDEL is 225° C. (437° F.). MXSTEN and the adhesive TIE BOND melt atmuch lower temperatures.

The hollow laminate following extrusion had an outside diameter of about0.5 inch (about 12.7 mm). The MXSTEN ply had an outside diameter ofabout 0.3 inch (about 7.62 mm). The thickness of the adhesive layer wasabout 0.05 inch (about 1.27 mm), and that of the outer ECDEL layer about0.15 inch (about 3.81 mm).

The corrugator had a linear speed of about 60′/min, and a forward run ofabout 4′. Expansion of the molten plastic laminate occurred in about thefirst few inches of travel; i.e., in about the first second followingextrusion, while the plastics were still molten. The molds had aninterior configuration identical to the exterior configuration of theboot seals of FIG. 1

Referring to FIG. 1, the manufactured (expanded) boot seals 12 had alarge end internal diameter of about 2 inches (about 47-50 mm), a smallend internal diameter of about 0.66 inch (about 16.9 mm), and acorrugated intermediate section between the large and small ends. Thecorrugated intermediate section had an outside diameter (peak-to-peak)of about 2.5 inches (about 63.4 mm) for most of its length except wheretapered at the end closest to the boot seal small end.

The distance between the peaks and valleys in the corrugatedintermediate section, and also in the tapered area, was about 0.5″(about 13.4 mm). This means that the boot seal laminate was expanded inthe corrugator 118 (FIG. 4) while molten about 400% for most of itslength, and to a minimum of about 130% at the boot seal small end.

The following Table gives approximate boot seal wall thicknesses atvarious points along the length of each seal.

TABLE 1 mm INCH Small end 3     .012 Corrugations near small end 2.3 0.9Corrugations in intermediate area 1.7 0.7 Large end 1.9 0.7

The reduced wall thicknesses of the expanded boot seal result primarilyfrom the diametrical expansion in the corrugator but also from somelongitudinal lengthening, particularly near the small end. Thereductions in wall thicknesses were greater in the areas of higherexpansion.

The molds of the corrugator functioned as a heat sink in the corrugatorforward run. The continuous extruded laminate had a temperature of about180°-200° F. at the time the molds were opened and the extruded laminatewas expelled from the corrugator. At this temperature, the laminate wasself-supporting, and was cooled in air to about 130° F., at which pointthe extruded laminate was cut into about 10 inch lengths suitable foruse in the apparatus of FIG. 2.

The manufactured boot seals have a flexural modulus which is about thesame as that of ECDEL, about 21,750 psi, well below the parameter of100,000 psi, and a percent elongation to break which is about the sameas that of ECDEL, about 400, well above the parameter of 100.

These data illustrate the excellent flex and elongation properties ofboot seals made according to the present invention.

At the same time, the boot seals have excellent toughness impartedprimarily by the expansion of the ECDEL ply, but also by the added bootseal thickness provided by the MXSTEN ply. As indicated above, MXSTENstretch-toughens as does ECDEL. This improved toughness is illustratedin Examples 2-4.

EXAMPLES 2-4

Corrugated tubular laminates were mold formed. The outer ply of eachcorrugated laminate contained an amount of ECDEL. The corrugatedlaminates were laboratory assembled and then laboratory stretched (atambient temperature) to evaluate the effect of stretch. They were testedfor strength using the puncture resistance test.

As shown in the following Table 2, both plies of the laminates containedamounts of MXSTEN. The purpose of this was to observe certain propertiesunrelated to the scope of the present invention.

The stretch procedure was carried out so that in the valleys of thecorrugations, the stretch was about 20%. At the peaks of thecorrugations, the stretch was about 320%.

Comparative data were obtained on mold formed samples composed ofSANTOPRENE. The comparative samples were not laminates and were notstretched as SANTOPRENE does not stretch-toughen.

The tubular samples of the present invention had the followingcompositions and ply-dimensions prior to stretching.

TABLE 2 Construction of MXSTEN/ECDEL Laminates Composition PlyComposition Ply Ex. of outer ply^(a) Thickness of Inner Ply Thickness 250% MXSTEN   0.015″ 100% MXSTEN   0.030″ 50% ECDEL (0.368 mm) (0.735 mm)3 90% MXSTEN   0.015″ 100% MXSTEN   0.030″ 10% ECDEL (0.368 mm) (0.735mm) 4 50% MXSTEN^(b)   0.015″ 100% MXSTEN   0.030″ 30% ECDEL (0.368 mm)(0.735 mm) ^(a)%'s by weight. ^(b)Example 4 contained 20% mineral fillerdispersed through the outer ply.

The plies in Examples 2, 3 and 4 were bonded together by Mitsui ChemicalCompany adhesive ADMER QB502A.

The following test data were obtained. The data given in the followingTable 3 are average data obtained from six samples in each Example.

TABLE 3 Puncture Resistance (PR of MXSTEN/ECDEL Laminates) 20% Stretch320% Stretch Example Tmm^(c) PR N/mm Tmm PR N/mm 2 1.13 56   0.43 150  3 1.19 52   0.48 128   4 1.14 53   0.47 129   SANTOPRENE 1.6  39.9 1.6  39.9 ^(c)Tmm is the average laminate wall thickness followingexpansion. In the case of SANTOPRENE, Tmm is the wall thickness of thesamples tested.

Even moderate stretching of samples in which a ply contains ECDEL (e.g.,20%) achieves an improvement in puncture resistance (PR) compared toSANTOPRENE. Substantial stretching (e.g., 320%) achieves a dramaticincrease in puncture resistance. Example 2 in which the outer ply was50% ECDEL provided better puncture resistance than Examples 3 and 4which contained 10% and 30% ECDEL respectively.

EXAMPLE 5

An advantage of the present invention is that the boot seal 12 of thepresent invention is resistant to dimensional changes induced bytemperature. Conventional stretch-strengthenable plastics which havebeen stretched tend to shrink when exposed to high temperatures. Powersteering linkages, and the boots installed to protect the linkages, gethot. The temperature can reach 175° C. The amount of shrink caused byhigh temperatures can cause the boots made of many plastics to interferewith the ball joints and/or other linkages over which they areinstalled. Interference between the boot and linkage protected by theboot likely accounts for a percentage of the failure modes observed withprior art boots.

Samples of boots made in accordance with the present invention wereexposed to different temperature for different periods of time. Theoutside diameter of the boots was measured by laser beam. The resultsare given in the following Table.

TABLE 4 Heating Times/Temperatures Effect On ECDEL Containing BootDiameter Time, Seconds Temperature, ° C. O.D., mm  0 Ambient 57.49 10120 57.58 30 120 57.56 60 120 57.62 10 131 57.61 30 131 57.63 10 19057.59

From Table 4, it can be seen that the boots of the present invention arevery heat-stable and did not to distort from heat-induced shrinkage.

Advantages of the present invention should be apparent. Primarily, theuse of a stretch-toughenable polyester thermoplastic elastomer which hasa flexural modulus of at least 100,000 psi and a percent elongation torupture of at least 100 provides a boot seal having greatly improvedproperties, particularly puncture resistance, compared to SANTOPRENE.Preferably, the resin is stretch-toughened to a puncture resistance ofat least 50 Newtons/mm of boot seal wall thickness. By using astretch-toughenable polyester resin such as ECDEL, the stretch-toughenedboot seal additionally is resistant to temperature induced shrinkage andthus failures caused by interference of the boot seal with the linkagebeing protected. Further, a polyester resin such as ECDEL advantageouslycan be extruded and vacuum molded in a continuous process such as thatdescribed with reference to FIGS. 4-8. This dramatically reduces thecost of manufacture compared to conventional blow molding procedureswhich are batch procedures.

By using the stretch-toughenable polyester resin as the outer ply in alaminated structure, wherein the inner ply is an extrudable resin whichis softer than the polyester resin, a boot seal is obtained which isboth strong and readily sealable with the linkage being protected.

EXAMPLE 6

An embodiment of the present is illustrated in FIG. 7B. FIG. 7Billustrates an extruder head 214 of an extruder die 216 positioned in amold cavity 218. The extruder head 214 is adapted for the co-extrusionof two-layers, an inner ply and outer ply. Instead of two layers, theextruder head 214 can be readily adapted for the extrusion of threelayers which include an intermediate bonding layer between the inner andouter plies.

The extruder head 214 includes a nozzle 220. The nozzle has acylindrical side wall 222 that extends from the die block (not shown) ofthe extruder die 216 along a central axis 224 to an open end 226. Thecylindrical side wall 222 has a cylindrical inner surface 228 and abeveled surface 230 at the open end 226 of the cylindrical side wall222.

An outer mandrel 232 is located in substantially coaxial relationshipwithin the cylindrical side wall 222 and is spaced from the cylindricalside wall 222. The outer mandrel 232 has a tube portion 234, a coneportion 236, and a flange portion 238. The tube portion 234 extends fromthe cone portion 236 of the outer mandrel 232 to the flange portion 238.The tube portion 234 has an outer cylindrical surface 240 and an innercylindrical surface 242. The outer cylindrical surface 240 of the tubeportion 234 and the inner cylindrical surface 228 of the cylindricalside wall 222 define a first passageway 244 through which a first moltenplastic stream flows from feed ports (not shown) of the extruder die216. The inner cylindrical surface 242 of the tube portion 234 of theouter mandrel 232 defines a second passageway 246 through which a secondmolten plastic stream flows from feed ports (not shown) of the extruderdie 216.

The cone portion 236 of the outer mandrel 232 extends through the openend 226 of the cylindrical side wall 222. The cone portion 236 of theouter mandrel 232 has an outer frustoconical surface 248 and an innerfrustoconical surface 250. The outer frustoconical surface 248 of theouter mandrel 232 and beveled surface 230 of the cylindrical side wall222 define a first annulus 252. The first annulus 252 is incommunication with the first passageway 244 so that, during extrusion,the first molten plastic stream that is in the first passageway 244flows from the first passageway 244 through the first annulus 252.

The flange portion 238 of the outer mandrel 232 is connected to a firstactuating means 260 that oscillates the outer mandrel 232 axially (leftand right directions as shown in FIG. 7B) relative to the cylindricalside wall 222. The first actuating means 260 can be any actuating meansknown in the art such as a pneumatic pressure cylinder mechanism.

Oscillation of the outer mandrel 232 causes the gap of the first annulus252 to increase or decrease. As the first molten plastic stream passesfrom the first passageway 244 through the increasing and decreasing gapof the first annulus 252, an outer ply 262 (FIG. 7C) is formed with avariable annular thickness. The outer ply 262 has alternating thinnerregions 262 a and thicker regions 262 b.

The extruder head 214 further includes an inner conical shaped mandrel266 that is located in substantially coaxial relationship within thecone portion 236 of the outer mandrel 232 and is spaced from the innerfrustoconical surface 250 of the outer mandrel 232. The inner conicalshaped mandrel 266 is attached to rod 268 that extends in a coaxialrelationship through the tube portion 234 of the outer mandrel 232. Theinner conical shaped mandrel 266 has a conical outer surface 270. Theconical outer surface 270 of the inner conical shaped mandrel 232 andthe inner frustoconical surface 250 of the outer mandrel 232 define asecond annulus 274. The second annulus 274 is in communication with thesecond passageway 246 so that during extrusion, the second moltenplastic stream in the second passageway 246 flows from the secondpassageway 246 through the second annulus 274 and forms an inner ply276.

The rod 268 is connected to a second actuating means 278 that oscillatesthe inner conical shaped mandrel 266. The second actuating means 278oscillates the inner conical shaped mandrel 266 axially (left and rightdirections as shown in FIG. 7B) relative to the outer mandrel 232. Thesecond actuating means 278 can be any actuating means 278 known in theart such as a pneumatic pressure cylinder mechanism.

Oscillation of the inner conical shaped mandrel 266 causes the gap ofthe second annulus 274 to increase or decrease. As the second moltenplastic stream passes from the second passageway 246 through theincreasing and decreasing gap of the second annulus 274, the inner ply276 (FIG. 7C) is formed with a variable annular thickness. The inner ply276 has alternating thinner regions 276 a and thicker regions 276 b.

The outer ply 262 and the inner ply 276 are extruded from the firstannulus 252 and second annulus 274, respectively, into the mold cavity218. During co-extrusion of the outer ply 262 and the inner ply 276, theoscillations of the outer mandrel 232 and the oscillations of the innerconical shaped mandrel 266 are synchronized. By synchronizing theoscillations of outer mandrel 232 and oscillations of the inner conicalshaped mandrel 266, the outer ply 262 and the inner ply 276 are extrudedwith the thicker regions 262 b of the outer ply 262 radially alignedwith the thicker regions 276 b of the inner ply 276. Duringco-extrusion, the oscillations of the outer mandrel 232 and theoscillations of the inner conical shaped mandrel 266 are alsosynchronized with the linear speed of the mold blocks 284 that travelalong the inner track (not shown) of the corrugator. By synchronizingthe oscillations of the outer mandrel 232 and inner conical shapedmandrel 266 with the linear speed of the mold blocks 284, the thickerregions 262 b and 276 b of the outer ply 262 and inner ply 276 can beradially aligned with the valleys 288 of the corrugated inner walls 290of the mold blocks 284.

FIG. 7C shows the extruded inner ply 276 and outer ply 262 in the moldcavity 218 prior to a vacuum being drawn in the mold cavity 218. Thethicker regions 262 b of the outer ply 262 are in contact with thethicker regions 276 b of the inner ply 276, and the thinner regions 262a of the outer ply 262 are in contact with the thinner regions 276 a ofthe inner ply 276. The thicker regions 276 b and 262 b of the inner ply276 and the outer ply 262 are radially aligned with the valleys 288 ofthe corrugated inner wall 290, and the thinner regions 276 a and 262 aof the inner ply 276 and the outer ply 262 are radially aligned with thepeeks 292 of the corrugated inner wall 290.

After the outer ply 262 and the inner ply 276 are extruded into the moldcavity 218, a vacuum is drawn in the corrugated inner wall 290 of moldblock 284. The extruded outer ply 262 and inner ply 276 expand radiallyagainst the peaks 292 and valleys 288 of the corrugated inner wall 290.The wall thicknesses of the outer ply 262 and inner ply 276 decrease asthe outer ply 262 and inner ply 276 expand against the peaks 292 andvalleys 288 of the corrugated inner wall 290. The degree of expansion ofthe outer ply 262 and inner ply 276 is greater along the valleys 288 ofthe corrugated inner wall 290 and less along the peaks 292 of thecorrugated inner wall 290. Hence, the wall thicknesses of the outer ply262 and inner ply 276 along the valleys 288 of the corrugated inner wall290 is thinned more than the wall thicknesses of the outer ply 262 andinner ply 276 along the peaks 292 of the corrugated inner wall 290.

The wall thicknesses of the expanded outer ply 262 and inner ply 276 areshown in FIG. 7D. FIG. 7D shows that outer ply 262 and the inner ply 276have uniform wall thicknesses longitudinally in the peaks 292 andvalleys 288 along the corrugated inner wall 290.

The advantage of this aspect of the method of FIGS. 7B, 7C, and 7D isthat the method provides a better means of control towards achievingmore uniform or desired flexural, elongation, and strength propertieslongitudinally along the length of the boot seal.

Although the extruder head 214 in Example 6 is illustrated with twoactuating means that oscillate both the outer mandrel 232 and the innerconical 266 shaped mandrel, the extruder head 214 may have only oneactuating means that oscillates the outer mandrel or the inner conicalshaped mandrel.

From the above description of the invention, those skilled in the artwill perceive improvements, changes and modifications. Suchimprovements, changes and modifications within the skill of the art areintended to be covered by the appended claims.

1. A process for making a boot seal comprising the steps of: (a)obtaining two plastics, at least one being a polyester resin; (b)feeding said plastics separately into an extruder die; (c) separatelyextruding said plastics from said extruder die as coaxial tubular moltenstreams, into a mold cavity having a corrugated inner wall; (d) vacuumexpanding the coaxial tubular molten streams against said mold cavityinner wall; (e) cooling the molten streams while vacuum held against themold cavity inner wall; and (f) stretching said polyester resin to causea molecular orientation for increasing the strength of said polyesterresin, said polyester resin, when cooled, being stretch toughened tohave a percent elongation to rupture of at least 100 and a flexuralmodulus less than 100,000 psi.
 2. The process of claim 1 wherein thesecond of said two plastics is a polyolefin, and an adhesive bondinglayer is co-extruded with and between said two molten streams.
 3. Theprocess of claim 1 wherein the two plastics are the same polyester resinand the plastic for the innermost molten stream of the coaxial moltenstreams contains a blowing agent.
 4. The process of claim 1 wherein thepolyester resin is a polyester material which is stretch toughenable toa puncture resistance of at least 50 Newtons/mm wall thickness.
 5. Theprocess of claim 1 wherein said vacuum expansion is at least 200%. 6.The process of claim 1 wherein said extrusion is continuous forming acontinuous series of boot seals which are separable by cuttingsubsequent to cooling.
 7. A boot seal made by the process of claim
 1. 8.A process of making a flexible part comprising the steps of: (a)obtaining two plastics, at least one being a polyester resin; (b)feeding said plastics separately into an extruder die; (c) separatelyextruding said plastics from said extruder die as molten streams into amold cavity having an inner wall of a desired shape; (d) vacuumexpanding the molten streams against said mold cavity inner wall; (e)cooling the molten streams while vacuum holds the molten streams againstthe mold cavity inner wall; and (f) stretching said polyester resin tocause molecular orientation for increasing the strength of saidpolyester resin, said polyester resin, when cooled, being stretchtoughened to have a percent elongation to rupture of at least 100 and aflexural modulus less than 100,000 psi.
 9. A process as set forth inclaim 8 wherein, said polyester resin is a material which is stretchtoughenable and said flexible part when cooled has a percent elongationto rupture of at least 100 and a flexural modulus less than 100,000 psi.10. The process of claim 9 wherein another of said plastics is athermoplastic elastomer which when expanded and cooled has a higherdegree of flexibility and softness than said polyester resin, saidpolyester resin when expanded and cooled being tougher and having agreater resistance to hydrocarbon chemicals than said thermoplasticelastomer.
 11. The process of claim 10 wherein said thermoplasticelastomer is a polyolefin.
 12. The process of claim 8 wherein saidplastics are extruded as coaxial tubular molten streams.